34762-17-9

Basic information

• Product Name: Diethyl2-(bromomethyl)malonate
• Synonyms: Diethyl2-(bromomethyl)malonate
• CAS NO: 34762-17-9
• Molecular Formula: C₈H₁₃BrO₄
• Molecular Weight: 253.09042
• Mol File: 34762-17-9.mol
• Article Data: 1

Chemical Properties

• Boiling Point: 235.444 °C at 760 mmHg
• Flash Point: 96.193 °C
• Appearance: /
• Density: 1.397 g/cm³
• Vapor Pressure: 0.05mmHg at 25°C
• Refractive Index: 1.468
• PKA: 11.13±0.46(Predicted)
• CAS DataBase Reference: Diethyl2-(bromomethyl)malonate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl2-(bromomethyl)malonate(34762-17-9)
• EPA Substance Registry System: Diethyl2-(bromomethyl)malonate(34762-17-9)

Safety Data

• Hazardous Substances Data: 34762-17-9(Hazardous Substances Data)

Usage

General Description

Diethyl 2-(bromomethyl)malonate, also known as bromoethyl diethylmalonate, is an organic compound and a derivative of malonic acid. It is a colorless liquid with a strong, fruity odor. This chemical is commonly used in organic synthesis as a versatile building block for the preparation of pharmaceuticals, agrochemicals, and other fine chemicals. Its reactivity and unique structure make it a valuable intermediate in the production of various complex organic compounds. Diethyl 2-(bromomethyl)malonate is also utilized in the research and development of new chemical processes and materials due to its wide range of potential applications. However, it is important to handle this compound with care, as it is classified as hazardous and should be used in a controlled environment with proper safety measures.

InChI:InChI=1/C8H13BrO4/c1-3-12-7(10)6(5-9)8(11)13-4-2/h6H,3-5H2,1-2H3

Synthetic route

diethyl ethoxymethylenemalonate (30379-04-5) → ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9)

Conditions	Yield
With hydrogen bromide In ethanol for 48h;	65%
With water; hydrogen bromide

diethyl methylenemalonate (3377-20-6) → ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9)

Conditions	Yield
With diethyl ether; hydrogen bromide

sodium diethylmalonate (996-82-7, 34727-00-9, 73177-21-6) → ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: diethyl ether 2: water; hydrobromic acid View Scheme

2-aminopyridine (504-29-0) + ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) → C13H18N2O4

Conditions	Yield
With potassium tert-butylate In tert-butyl alcohol at -20 - -15℃; for 8.5h; Solvent; Temperature; Reagent/catalyst;	91.7%

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + ethyl 3-hydroxyphenylacetate (22446-38-4) → C18H24O7 (1289544-57-5)

Conditions	Yield
Stage #1: ethyl 3-hydroxyphenylacetate With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.333333h; Inert atmosphere; Stage #2: ethyl 3-bromo-2-(ethoxycarbonyl)propionate In N,N-dimethyl-formamide at 110℃; Inert atmosphere;	65%

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + methylamine hydrochloride (593-51-1) → 2,2'-(2-methyl-2-aza-propanediyl)-di-malonic acid tetraethyl ester

Conditions	Yield
With ethanol; silver(l) oxide

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + potassium phtalimide (1074-82-4) → phthalimidomethyl-malonic acid diethyl ester (5101-83-7)

Conditions	Yield
With xylene

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) → diethyl 2-azido-2-methylmalonate (849114-26-7)

Conditions	Yield
With sodium azide; ethanol

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + triphenylphosphine (603-35-0) → (2,2-Bis-ethoxycarbonyl-ethyl)-triphenyl-phosphonium; bromide (34762-20-4)

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + <1>isoquinolyl-methyl lithium → (2-[1]isoquinolyl-ethyl)-malonic acid diethyl ester (101719-34-0)

Conditions	Yield
With diethyl ether

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + acetic acid (64-19-7) + zinc → methyl-propanedioic acid (516-05-2)

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) → bromo-phthalimidomethyl-malonic acid diethyl ester

Conditions	Yield
Multi-step reaction with 2 steps 1: xylene 2: chloroform; bromine View Scheme

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + N-[(1R)-1-methyl-2-propen-1-yl]-2-pyridinesulfonamide (861848-44-4) → C17H24N2O6S

Conditions	Yield
With caesium carbonate In 1-methyl-pyrrolidin-2-one at 115℃; for 17h; Inert atmosphere; Large scale reaction;

ethyl 3-bromo-2-(ethoxycarbonyl)propionate (34762-17-9) + 1-benzyl-3-hydroxy-1H-indazole (2215-63-6) → diethyl 2-(((1-benzyl-1H-indazol-3-yl)oxy)methyl)malonate

Conditions	Yield
Stage #1: 1-benzyl-3-hydroxy-1H-indazole With potassium carbonate In 1,2-dimethoxyethane at 20℃; for 0.166667h; Stage #2: ethyl 3-bromo-2-(ethoxycarbonyl)propionate In 1,2-dimethoxyethane for 4h; Reflux;

Upstream product

• 996-82-7 sodium diethylmalonate 
• 30379-04-5 diethyl ethoxymethylenemalonate 
• 3377-20-6 diethyl methylenemalonate 

Downstream Products

• 34762-20-4 (2,2-Bis-ethoxycarbonyl-ethyl)-triphenyl-phosphonium; bromide 
• 1289544-57-5 C₁₈H₂₄O₇ 
• 516-05-2 methyl-propanedioic acid 

Relevant articles and documents

277. Structure and Chemistry of Malonylmethyl- and Succinyl-Radicals. The Search for Homolytic 1,2-Rearrangements

Malonylmethyl radical I and its thioester analogue II were generated by standard photolytic and thermolytic methods from perester and bromo precursors.The structures of I and II were examined by ESR spectroscopy and found to exist in preferred conformations.However, no indication for their rearrangement by 1,2-shift of either an ethoxycarboxyl or (ethylthio)carbonyl group to the corresponding succinyl radicals III and IV, respectively, was found at temperatures below -40 deg C.At higher temperatures of up to 140 deg C, the search for malonylmethyl -> succinyl rearrangement was examined by thorough-product analysis of the perester decomposition.There is evidence for the rearrangement of the radical I to III by photolysis and of the radical II to IV by thermolysis at 130 deg C in chlorobenzene to only a small extent.